Azomethine pigments

ABSTRACT

Azomethine pigments of the formula ##STR1## and metal complexes thereof, wherein A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, an alkyl group containing 1-6 C atoms, or an aryl radical, X 2  and X 4  denote H atoms or halogen atoms, X 1  and X 3  denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X 1  -X 4  also to be a nitro group which are useful for pigmenting of high molecular material.

This is a division of application Ser. No. 502,246, filed on Aug. 30, 1974, now U.S. Pat. No. 3,974,149.

It has been found that new, valuable azomethine pigments of the formula ##STR2## wherein A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, an alkyl group containing 1-6 C atoms, or an aryl radical, X₂ and X₄ denote H atoms or halogen atoms, X₁ and X₃ denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X₁ -X₄ also to be a nitro group, are obtained if

A. AN ISOINDOLINONE HYDRAZONE OF THE FORMULA ##STR3## particularly an isoindolinone hydrazone of the formula ##STR4## wherein X₅ and X₇ denote H atoms or chlorine atoms or alkoxy groups containing 1-4 C atoms, X₆ and X₈ denote H atoms or chlorine atoms, X₆ and X₈ representing chlorine atoms if X₅ and X₇ denote alkoxy groups, is condensed with a compound of the formula ##STR5## wherein Q denotes an O atom or an imino group, or

b. an isoindolinone of the formula ##STR6## wherein V denotes a group of the formula ##STR7## wherein Z₁ denotes an imino or thio group and the Z₂ 's denote halogen atoms, or alkoxy or secondary amino groups, is condensed with a hydrazone of the formula ##STR8## and the resulting azomethine is optionally metallised.

Azomethine pigments of particular interest are those of the formula ##STR9## wherein M denotes a divalent metal atom and A, R and X₁ -X₄ have the meaning indicated, and particularly those of the formula ##STR10## wherein A₁ denotes a benzene, pyridine, pyrimidine or pyrane radical which can also contain a fused benzene nucleus, or denotes a pyrazolone radical, M₁ denotes a copper or nickel atom, X₅ to X₈ have the meaning indicated and R₁ denotes a hydrogen atom or the methyl group.

Azomethine pigments which are particularly preferred are those of the formula ##STR11## wherein R₁, M₁ and X₅ to X₈ have the meaning indicated above, Y₃ and Y₄ denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro groups or groups of the formula ##EQU1## wherein M₂ denotes a Ca, Sr, Ba or Mn atom, and Z represents an O atom or an imino group, and particularly those of the formula ##STR12## wherein Z₃ denotes a hydroxyl or methyl group, and R₁, M₁, X₅ to X₈, Y₃ and Y₄ have the meaning indicated above.

Azomethine pigments of particular interest are also those of the formula ##STR13## wherein M₁ and X₅ to X₈ have the meaning indicated above, Y₁ denotes a H atom, a carboxyl group, a carbamoyl group, an alkoxycarbonyl or alkylcarbamoyl group containing 2-6 C atoms, a phenylcarbamoyl group which is optionally substituted in the phenyl radical by halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or by trifluoromethyl groups, or a group of the formula ##EQU2## wherein M₂ has the meaning indicated above, and Y₂ denotes a H atom or halogen atom, an alkoxy group containing 1-4 C atoms, a nitro group or a nitrile group, those of the formula ##STR14## wherein R₂ denotes an alkyl group of 1-4 C-atoms, preferably a methyl group, or an optionally substituted aryl group, those of the formula ##STR15## wherein R₃ denotes a nitrile or carbamoyl group, those of the formula ##STR16## wherein R₄ denotes a nitrile or carbamoyl group, those of the formula ##STR17## wherein R₅ denotes a H atom, an alkyl group containing 1-4 C atoms, or an aryl group, or those of the formula ##STR18## wherein M₁ and X₅ to X₈ have the meaning indicated above and R₆ denotes an alkyl group containing 1-4 C atoms, an alkoxycarbonyl group containing 2-5 C atoms, a carboxyl group, a carbamoyl group or a group of the formula ##EQU3## wherein M₂ denotes a Ca, Sr, Ba or Mn atom, and Y₅ and Y₆ denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro, acylamino, carbamoyl or sulphamoyl groups or groups of the formula ##EQU4## wherein M₂ denotes a Ca, Sr, Ba or Mn atom.

The isoindolinone hydrazones used as starting materials are obtained by reacting hydrazine with an isoindolinone of the formula ##STR19## particularly an isoindolinone of the formula ##STR20## X₁ -X₈ and V in the formulae indicated having the indicated meaning.

It is preferable to start from 3-imino-isoindolinone or from 3,3'-dialkoxy-iminoisoindolinones of the formula ##STR21## wherein X₅ to X₈ have the meaning indicated and R₃ denotes an alkyl group containing 1-4 C atoms. Those starting materials wherein X₅ to X₈ denote chlorine atoms or hydrogen atoms, are known, and those wherein X₅ and X₇ denote alkoxy, cycloalkoxy, aralkoxy, aryloxy, alkylthio or arylthio groups and X₆ and X₈ denote chlorine atoms, can be obtained by reacting an ammonium salt or ester of tetrachloro-o-cyanobenzoic acid in a hydrophilic organic solvent with a compound of the formula X₅ M₃ wherein X₅ has the meaning indicated above and M₃ denotes an alkali metal atom, and esterifying the product obtained, if necessary.

The following examples of isoindolinones may be mentioned: 3,3-Dimethoxy-4,5,6,7-tetrachloro-isoindolinone, 3,3-dimethoxy-4,5,6,7-tetrabromo-isoindolinone, 3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-butoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(p-chlorophenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(o-methylphenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-methylmercapto-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-ethylmercapto-isoindolinone, 3,3,4,6-tetramethoxy-5,7-dichloro-isoindolinone and 3-imino-isoindolinone.

The hydrazones of the isoindolinones mentioned are condensed with compounds of the formula ##STR22## wherein Q denotes an O atom or an imino group, for example a phenylimino group, especially with aldehydes of the formula ##STR23## A and R in the formula indicated having the abovementioned meaning.

Aldehydes or ketones of particular interest are those of the formula ##STR24## wherein R₁ denotes a hydrogen atom or the methyl group, and Y₃, Y₄ and Z have the meaning indicated, and especially the hydroxyquinoline aldehydes of the formula ##STR25## wherein R₁, Y₃, Y₄ and Z₃ have the meaning indicated.

Aldehydes of particular interest are also those of the following formulae ##STR26## wherein R₃ denotes a nitrile or carbamoyl group and R₂ denotes a lower alkyl group or an aryl group, ##STR27## wherein R₄ has the same meaning as R₃, ##STR28## wherein Y₃ and Y₄ have the meaning indicated above and R₅ denotes a H atom, a lower alkyl group or an aryl group, hydroxynaphthaldehydes of the formula ##STR29## wherein Y₁ and Y₂ have the meaning indicated above, or pyrazolone aldehydes of the formula ##STR30## wherein R₆, Y₅ and Y₆ have the meaning indicated above. In the above formulae 22 to 29, the aldehyde group can also be replaced by an azomethine group of the formula --CR₁ =Q or --CH=Q wherein Q preferably denotes the phenylimino group.

The following aldehydes or ketones may be mentioned as examples:

1. o-Hydroxybenzaldehydes

Salicylaldehyde, 4-chloro-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 3-nitro-2-hydroxybenzaldehyde, 5-nitro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 3,5-dibromo-2-hydroxybenzaldehyde, 5-phenylazo-2-hydroxybenzaldehyde, 5-(2'-chloro-phenylazo)-2-hydroxybenzaldehyde, 5-(2',5'-dichlorophenylazo)-2-hydroxybenzaldehyde, 5-(2'-methyl-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methoxy-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methoxy-4'-nitro-phenylazo)-2-hydroxybenzaldehyde and 5-(2'-methoxy-5'-carbamoyl-phenylazo)-2-hydroxybenzaldehyde.

2. Hydroxynaphthaldehydes

2-Hydroxynaphthaldehyde, 6-bromo-2-hydroxynaphthaldehyde, 5-nitro-2-hydroxynaphthaldehyde, 2-hydroxy-3-carboxy-naphthaldehyde, 2-hydroxy-3-methoxycarbonyl-naphthaldehyde, 2-hydroxy-3-phenylcarbamoyl-naphthaldehyde, 2-hydroxy-3-(4'-chlorophenylcarbamoyl)naphthaldehyde, 2-hydroxy-3-(4'-chloro-2'-methylphenylcarbamoyl-naphthaldehyde, 2-hydroxy-3-(2',5'-dimethoxy-3'-chloro-phenylcarbamoyl-naphthaldehyde, 2-hydroxy-6-bromo-3-carboxynaphthaldehyde and 2-hydroxy-6-bromo-3-phenylcarbamoylnaphthaldehyde.

3. Heterocyclic aldehydes and ketones

2,6-Dihydroxy-4-methyl-5-cyano-3-pyridine aldehyde, 2,6-dihydroxy-4-methyl-5-carboxy-3-pyridine aldehyde, 2,6-dihydroxy-4-methyl-5-carbamoyl-3-pyridine aldehyde, 2,4-dihydroxy-3-quinoline aldehyde, 5-chloro-2,4-dihydroxy-3-quinoline aldehyde, 6-chloro-2,4-dihydroxy-3-quinoline aldehyde, 7-chloro-2,4-dihydroxy-3-quinoline aldehyde, 8-chloro-2,4-dihydroxy-3-quinoline aldehyde, 6,8-dichloro-2,4-dihydroxy-3-quinoline aldehyde, 7,8-dichloro-2,4-dihydroxy-3-quinoline aldehyde, 6-methyl-2,4-dihydroxy-3-quinoline aldehyde, 7-methyl-2,4-dihydroxy-3-quinoline aldehyde, 8-methyl-2,4-dihydroxy-3-quinoline aldehyde, 6-chloro-8-methyl-2,4-dihydroxy-3-quinoline aldehyde, 2,4-dihydroxy-3-acetyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-quinoline, 2,4-dihydroxy-3-acetyl-6-chloro-quinoline, 3-hydroxy-4-isoquinolone aldehyde, N-methyl-3-hydroxy-4-isoquinoline aldehyde, N-phenyl-3-hydroxy-4-isoquinoline aldehyde, N-naphthyl-3-hydroxy-4-isoquinolone aldehyde, 2-methyl-4,6-dihydroxy-5-pyrimidine aldehyde, 2-phenyl-4,6-dihydroxy-5-pyrimidine aldehyde, 4-hydroxy-3-quinaldine aldehyde, 6-chloro-4-hydroxy-3-quinaldine aldehyde, 6-methoxy-4-hydroxy-3-quinaldine aldehyde and further aldehydes.

4-Hydroxycoumarin-3-aldehyde, 1-phenyl-3-methyl-4-formylpyrazolone- 5,1-phenyl-3-carboxy-4-formylpyrazolone-5,1-phenyl-3-methoxycarbonyl-4-formylpyrazolone- 5,1-phenyl-3-ethoxycarbonyl-4-formylpyrazolone- 5,1-(2'-chlorophenyl)-3-methyl-4-formylpyrazolone- 5,1-(4'-chlorophenyl)-3-methyl-4-formylpyrazolone- 5,1-(2'-methylphenyl)-3-methyl-4-formylpyrazolone-5 and 1-(4'-methylphenyl)-3-methyl-4-formylpyrazolone-5.

Instead of the aldehydes or ketones, it is also possible to use imines, particularly phenylimines, thereof.

For the embodiment (b) of the process according to the invention, the starting materials used are appropriately, on the one hand, isoindolinones of the formula 20), particularly those of the formula 21), and, on the other hand, hydrazones of the aldehydes or ketones of the formulae 22-29).

The condensation of the hydrazone with the oxo compound or the isoindolinone is appropriately carried out in water or an organic solvent, at an elevated temperature, preferably between 50° C and the boiling point of the solvent used. The following examples of solvents may be mentioned: water, alcohol, glacial acetic acid, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, butyrolactone, glycol monomethyl ether, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or mixtures thereof.

As the resulting azomethines are sparingly soluble in the solvents mentioned, they can be isolated easily by filtration. Impurities which may be present can be removed by washing.

For conversion into the metal complexes, the azomethines obtained are treated with agents which donate divalent metals, for example with salts of zinc, manganese, cobalt or iron, but particularly of copper and nickel, or of mixtures of such metals. The formates, acetates or stearates of these metals are preferably used. The metallisation is appropriately carried out in one of the abovementioned solvents.

The metallisation can also be carried out at the same time as the condensation, by condensing the aldehyde together with the hydrazone in one of the abovementioned solvents, in the presence of metal salts.

The metal complexes often additionally contain 0.5-2 mols of water of crystallisation, which, in appropriate instances, exerts a slight influence on the shade of the colorant obtained.

The new colorants represent valuable pigments which can be used, in a finely dispersed form, for pigmenting high molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, individually or as mixtures.

It is immaterial here whether the high molecular compounds mentioned are present as plastic compositions or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the application, it is found to be advantageous to use the new pigments as toners or in the form of preparations.

The resulting colorations are distinguished by good fastness to light and migration.

In the following examples, unless otherwise specified, the parts denote parts by weight, and the percentages denote percentages by weight.

A. PREPARATION OF THE COMPLEX-FORMING AGENTS EXAMPLE 1

119.6 g of 3,4,5,6-tetrachloro-2-cyanobenzoic acid methyl ester are dissolved in 600 ml of methanol and 70.6 g of a 30.6% strength methanolic solution of Na methylate. The solution is cooled to 10° C and is added dropwise at 10° C to a solution of 200 ml of hydrazine hydrate in 400 ml of methanol. A yellowish precipitate is formed. The reaction mixture is stirred at room temperature for 2 hours and is then warmed to 35° C over the course of 30 minutes and 200 ml of glacial acetic acid are added at this temperature. After stirring for 1 hour at room temperature, the product is filtered off and the filter residue is washed with methanol and water. The material filtered off is then extracted by boiling in 1 l of methylcellosolve for a further 2 hours, filtered off at room temperature and washed with methylcellosolve and methanol. After drying at 70° C, 98 g (82% of theory) of analytically pure 4,5,6,7-tetrachloro-isoindolin-1-on- 3-ylidene hydrazine of the formula ##STR31## are obtained.

In an analogous manner, 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine is obtained in 87% yield from 4,6-dichloro-3,5-dimethoxy-2-cyanobenzoic acid methyl ester, 4,5,7-trichloro-6-methoxy-isoindolin-1-ylidene-3-hydrazine is obtained in 91% yield from 3,5,6-trichloro-4-methoxy-2-cyanobenzoic acid methyl ester and 4,5,7-trichloro-6-phenoxy-isoindolin-1-on-3-ylidene hydrazine is obtained in 67% yield from 3,4,6-trichloro-5-phenoxy-2-cyanobenzoic acid methyl ester.

4.49 g of tetrachloro-isoindolin-1-ylidene-3-hydrazine and 4.36 g of 1-formyl-2-hydroxy-3-naphthoic acid anilide in 250 ml of methylcellosolve are heated under reflux for 30 minutes. The thick, yellow precipitate is filtered off at 80° C, washed well with methylcellosolve, alcohol and acetone and dried at 80° C. 8.3 g (97% of theory) of the analytically pure colorant of the formula ##STR32## are obtained. Instead of methylcellosolve, Carbitols, dimethylformamide or glacial acetic acid can also be used.

The azomethines of the following formula ##STR33## wherein the symbols have the meaning indicated in the following table, are obtained by an analogous process.

                                      Table I                                      __________________________________________________________________________     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                          X.sub.3                                                                            X.sub.4                                                                          Y.sub.1     Y.sub.2                                                                          R Shade                                                                              Yield                                     __________________________________________________________________________     2    Cl  Cl                                                                               Cl  Cl                                                                               H           H H yellow                                                                             94%                                       3    Cl  Cl                                                                               Cl  Cl                                                                               COOH        H H yellow                                                                             78%                                       4    Cl  Cl                                                                               Cl  Cl                                                                                ##STR34##  H H orange                                                                             74%                                       5    Cl  Cl                                                                               Cl  Cl                                                                               COOH        Br                                                                               H yellow                                                                             75%                                       6    CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               COOH        H H yellow                                                                             87%                                       7    CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               COOH        Br                                                                               H yellow                                                                             89%                                       8    CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H           H H yellow                                                                             87%                                       9    CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                                ##STR35##  H H yellow                                                                             90%                                       __________________________________________________________________________

EXAMPLE 10

5.98 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 3.78 g of 2,4-dihydroxy-quinoline-3-aldehyde in glacial acetic acid are boiled under reflux for 5 minutes. The yellow precipitate is filtered off at room temperature, washed well with glacial acetic acid, alcohol and acetone and dried at 80° C. 8.2 g (87% of theory) of the analytically pure pigment of the formula ##STR36## are obtained. The hydrazones of the following formula ##STR37## wherein the symbols have the meaning indicated in Table II which follows, are obtained by an analogous process.

                                      Table II                                     __________________________________________________________________________     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                          X.sub.3                                                                            X.sub.4                                                                          Y.sub.7                                                                          Y.sub.8                                                                           Y.sub.9                                                                           Y.sub.10                                                                          R  Shade                                                                              Yield                                       __________________________________________________________________________     11   Cl  Cl                                                                               Cl  Cl                                                                               H Cl H  H  H  yellow                                                                             95%                                         12   Cl  Cl                                                                               Cl  Cl                                                                               H CH.sub.3                                                                          H  H  H  yellow                                                                             92%                                         13   Cl  Cl                                                                               Cl  Cl                                                                               H H  Cl Cl H  yellow                                                                             90%                                         14   Cl  Cl                                                                               Cl  Cl                                                                               Cl                                                                               H  H  Cl H  yellow                                                                             67%                                         15   Cl  Cl                                                                               Cl  Cl                                                                               H H  H  H  CH.sub.3                                                                          yellow                                                                             77%                                         16   Cl  Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H  H  H  yellow                                                                             86%                                         17   Cl  Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H  H  H  yellow                                                                             91%                                         18   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H  H  H  yellow                                                                             78%                                         19   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H CH.sub.3                                                                          H  H  H  yellow                                                                             92%                                         20   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H  H  H  yellow                                                                             85%                                         21   Cl  Cl                                                                               Cl  Cl                                                                               H Cl H  H  CH.sub.3                                                                          yellow                                                                             81%                                         22   Cl  Cl                                                                               Cl  Cl                                                                               H CH.sub.3                                                                          H  H  CH.sub.3                                                                          yellow                                                                             67%                                         23   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H  H  CH.sub.3                                                                          yellow                                                                             91%                                         24   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H  H  CH.sub.3                                                                          yellow                                                                             82%                                         25   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H CH.sub.3                                                                          H  H  CH.sub.3                                                                          yellow                                                                             93%                                         26   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H  H  H  yellow                                                                             91%                                         27   Cl  Cl                                                                               Cl  Cl                                                                               H H  Cl Cl CH.sub.3                                                                          yellow                                                                             82%                                         28   Cl  Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  H  H  CH.sub.3                                                                          yellow                                                                             87%                                         29   CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  Cl Cl CH.sub.3                                                                          yellow                                                                             97%                                         30   CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  Cl Cl H  yellow                                                                             91%                                         31   Cl  Cl                                                                               PhO Cl                                                                               H H  H  H  CH.sub.3                                                                          yellow                                                                             87%                                         32   Cl  Cl                                                                               PhO Cl                                                                               H H  H  H  H  yellow                                                                             94%                                         __________________________________________________________________________

EXAMPLE 33

14.50 g of 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine and 13.2 g of 2,4-dihydroxyquinoline-3-N-phenylaldimine in 250 ml of methylcellosolve are boiled under reflux for 1 hour. The yellow precipitate is filtered off at 100° C, washed well with alcohol and dried at 80° C (under vacuum). 18.75 g (82% of theory) of the analytically pure bishydrazine are obtained.

The following hydrazones, for example, are obtained by an analogous process:

                                      Table III                                    __________________________________________________________________________     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                          X.sub.3                                                                            X.sub.4                                                                          Y.sub.7                                                                          Y.sub.8                                                                          Y.sub.9                                                                          Y.sub.10                                                                          R  Shade                                                                              Yield                                         __________________________________________________________________________     34   Cl  Cl                                                                               Cl  Cl                                                                               H Cl                                                                               H H  CH.sub.3                                                                          yellow                                                                             72%                                           35   CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H Cl                                                                               H H  CH.sub.3                                                                          yellow                                                                             82%                                           __________________________________________________________________________

EXAMPLE 36

10.95 g of imino-isoindolinone hydrochloride and 12.18 g of the hydrazone of 2,4-dihydroxyquinoline-3-aldehyde are boiled for 5 minutes with 99 g of sodium acetate in 250 ml of glacial acetic acid. The yellow suspension is filtered at 80° C and the precipitate is washed well with glacial acetic acid, alcohol and acetone and dried at 80° C. 16.8 g (84% of theory) of the analytically pure bishydrazone are obtained.

The following bishydrazones, for example, are obtained by an analogous process:

                  Table IV                                                         ______________________________________                                         Ex.                                                                            No.   X.sub.1                                                                              X.sub.2                                                                              X.sub.3                                                                            X.sub.4                                                                            Y.sub.7                                                                            Y.sub.8                                                                            Y.sub.9                                                                            Y.sub.10                                                                            R    Shade Yield                    ______________________________________                                         37    H     H     H   H   H   H   H   H    CH.sub.3                                                                            yellow                                                                               75%                      38    H     H     H   H   H   Cl  H   H    CH.sub.3                                                                            yellow                                                                               77%                      ______________________________________                                    

EXAMPLE 39

5.98 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 4.04 g of 1-phenyl-3-methyl-4-formyl-pyrazolone-5 in 200 ml of alcohol are heated under reflux for one hour. The yellow suspension is filtered while warm and the filter residue is washed well with alcohol and dried at 80° C. 9.2 g (95% of theory) of the analytically pure pigment of the formula ##STR38## are obtained.

The hydrazones of the following formula ##STR39## wherein the symbols have the meaning indicated in Table V which follows, are obtained by an analogous process.

                                      Table V                                      __________________________________________________________________________     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                          X.sub.3                                                                            X.sub.4                                                                           X.sub.5                                                                           Y.sub.6                                                                           R.sub.6                                                                              Shade                                                                               Yield                                       __________________________________________________________________________     40   Cl  Cl                                                                               Cl  Cl Cl H  CH.sub.3                                                                             yellow                                                                               86%                                        41   OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl Cl H  COOC.sub.2 H.sub.5                                                                   yellow                                                                               68%                                        42   Cl  Cl                                                                               Cl  Cl H  H  CH.sub.3                                                                             yellow                                                                              100%                                        43   CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl H  CH.sub.3                                                                          CH.sub.3                                                                             yellow                                                                              100%                                        44   Cl  Cl                                                                               Cl  Cl H  CH.sub.3                                                                          CH.sub.3                                                                             yellow                                                                              100%                                        45   CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl H  H  CONH.sub.2                                                                           yellow                                                                               73%                                        __________________________________________________________________________

EXAMPLE 46

15.00 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 13.25 g of the anil of 4-hydroxycoumarin-3-aldehyde are suspended in 350 ml of methylcellosolve and heated at 100° C for 1 hour. The resulting yellow precipitate is filtered off at room temperature, washed with methylcellosolve, alcohol and acetone and dried at 80° C. 22.3 g (95% of theory) of the colorant of the formula ##STR40## are obtained.

EXAMPLE 47

A colorant having similar properties is obtained if 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine is used as the starting material. The yield is 75% of theory.

The bishydrazones described in Examples 1 - 30 can also be prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones.

EXAMPLE 48

14.5 g of 5,7-trichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine are suspended in a finely dispersed form in 200 ml of methylcellosolve and heated to 70° C. 11.6 g of 1-phenyl-3-carboxy-4-formyl-pyrazolone-5 in 150 ml of methylcellosolve are added slowly to this suspension. The reaction mixture is then kept at 100° C for 2 hours. After cooling to room temperature, the yellow crystals precipitated are filtered off, washed with a little methylcellosolve, with alcohol and acetone and dried at 80° C. 14.7 g (59% of theory) of the analytically pure compound of the formula ##STR41## are obtained.

EXAMPLE 49

An analogous compound is obtained in 72% yield, if the instructions of Example 48 are followed, but the starting material is 4,5,6,7-tetrachloro-isoindolin-1-on-3-ylidene hydrazine.

EXAMPLES 50-55

The bishydrazones of the following formula are obtained if the process of Example 10 is followed, using 2-methyl-4-hydroxy-quinoline-3-aldehyde instead of 2,4-dihydroxyquinoline-3-aldehyde. ##STR42##

The meaning of the symbols is indicated in Table VI which follows.

                  Table VI                                                         ______________________________________                                         Example                                                                        No.    X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                            Y.sub.3                                                                              Shade  Yield                             ______________________________________                                         50     Cl      Cl     Cl    Cl  H     yellow 97%                               51     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl  H     yellow 84%                               52     Cl      Cl     Cl    Cl  OCH.sub.3                                                                            yellow 94%                               53     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl  CH.sub.3 O                                                                           yellow 89%                               54     Cl      Cl     Cl    Cl  Cl    yellow 94%                               55     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl  Cl    yellow 92%                               ______________________________________                                    

EXAMPLES 56-57

The bishydrazones of the formula which follows are obtained analogously if a 4,6-dihydroxypyrimidine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10. The meaning of the symbols is given in Table VII.

                  Table VII                                                        ______________________________________                                          ##STR43##                                                                     Example                                                                        No.    X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                            R    Shade  Yield                              ______________________________________                                         56     Cl      Cl     Cl    Cl  CH.sub.3                                                                            yellow 84%                                57     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl  CH.sub.3                                                                            yellow 81%                                ______________________________________                                    

EXAMPLES 58-63

The bishydrazones of the following formula are obtained analogously if a 4,6-dihydroxypyrimidine-5-N-phenylaldimine is used instead of 2,4-dihydroxyquinoline-3-N-phenylaldimine in the process of Example 33.

    ______________________________________                                          ##STR44##                                                                     Example                                                                        No.    X.sub.1 X.sub.2                                                                              X.sub.3                                                                              X.sub.4                                                                             R    Shade  Yield                              ______________________________________                                         58     Cl      Cl    Cl    Cl   H    yellow 78%                                59     Cl      Cl    CH.sub.3 O                                                                           Cl   H    yellow 92%                                60     CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl   H    yellow 85%                                61     Cl      Cl    Cl    Cl   CH.sub.3                                                                            yellow 86%                                62     Cl      Cl    CH.sub.3 O                                                                           Cl   CH.sub.3                                                                            yellow 85%                                63     CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl   CH.sub.3                                                                            yellow 73%                                ______________________________________                                    

EXAMPLES 64-67

The bishydrazones of the following formula are obtained analogously if a 2,6-dihydroxy-pyridine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10.

    ______________________________________                                          ##STR45##                                                                     Example                                                                        No.    X.sub.1 X.sub.2                                                                              X.sub.3                                                                              X.sub.4                                                                            R     Shade  Yield                              ______________________________________                                         64     Cl      Cl    Cl    Cl  CN    yellow 94%                                65     CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CN    yellow 86%                                66     Cl      Cl    Cl    Cl  CONH.sub.2                                                                           yellow 73%                                67     CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CONH.sub.2                                                                           yellow 68%                                ______________________________________                                    

EXAMPLES 68-70

The bishydrazones of the following formula are obtained analogously if a benzimidazolo-6-hydroxypyridine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10

    ______________________________________                                          ##STR46##                                                                     Example                                                                        No.    X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R     Shade Yield                             ______________________________________                                         68     Cl      Cl     Cl    Cl   CN    orange                                                                               92%                               69     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN    yellow                                                                               88%                               70     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CONH.sub.2                                                                           yellow                                                                               76%                               ______________________________________                                    

EXAMPLES 71-88

The bishydrazones of the formula which follows are prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones of 3-hydroxy-isoquinolone-4-aldehyde. The meaning of the symbols is given in the table.

    __________________________________________________________________________      ##STR47##                                                                     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           R             Shade                                                                              Yield                                     __________________________________________________________________________                                      yellow-                                       71   Cl  Cl Cl  Cl H             orange                                                                             68%                                       72   Cl  Cl CH.sub.3 O                                                                         Cl H             orange                                                                             91%                                       73   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H             yellow                                                                             80%                                       74   Cl  Cl Cl  Cl CH.sub.3      orange                                                                             75%                                       75   Cl  Cl CH.sub.3 O                                                                         Cl CH.sub.3      yellow                                                                             90%                                       76   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl CH.sub.3      yellow                                                                             69%                                       77   Cl  Cl Cl  Cl                                                                                 ##STR48##    yellow                                                                             87%                                       78   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR49##    yellow                                                                             90%                                       79   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR50##    yellow                                                                             65%                                       80   Cl  Cl Cl  Cl                                                                                 ##STR51##    yellow                                                                             89%                                       81   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR52##    yellow                                                                             90%                                       82   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR53##    yellow                                                                             65%                                       83   Cl  Cl Cl  Cl                                                                                 ##STR54##    yellow                                                                             87%                                       84   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR55##    yellow                                                                             86%                                       85   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR56##    yellow                                                                             60%                                       86   Cl  Cl Cl  Cl                                                                                 ##STR57##    orange                                                                             94%                                       87   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR58##    yellow                                                                             85%                                       88   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR59##    orange                                                                             82%                                       __________________________________________________________________________

B. PREPARATION OF THE METAL COMPLEXES EXAMPLE 89

1.72 g of the bishydrazone from Example 1 are reacted, in 70 ml of methylcellosolve, with 0.83 g of Ni(ac)₂.4H₂ O for 4 hours at 90° C. The orange reaction product is filtered off while warm, washed well with methylcellosolve, alcohol and acetone and dried at 80° C. 1.65 g (87%) are obtained of an orange pigment of the formula ##STR60## which colours PVC in orange shades of good fastness to light and migration. The metallisation can also be carried out, for example, in dimethylformamide or Carbitol. The following metal complexes are prepared by an analogous process: ##STR61##

                                      Table VIII                                   __________________________________________________________________________     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.1      Y.sub.2                                                                           M  Shade                                    __________________________________________________________________________      90  Cl  Cl Cl  Cl H            H  Cu orange                                    91  Cl  Cl Cl  Cl H            H  Zn orange                                    92  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H            H  Ni orange                                    93  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H            H  Cu brown                                     94  Cl  Cl Cl  Cl COOH         H  Ni orange                                    95  Cl  Cl Cl  Cl COOH         H  Zn orange                                    96  Cl  Cl Cl  Cl COOH         H  Cd yellow                                    97  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH         H  Ni orange                                    98  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH         H  Cu yellow                                    99  Cl  Cl Cl  Cl COOH         Br Ni orange                                   100  Cl  Cl Cl  Cl COOH         Br Cu yellow                                   101  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH         Br Ni yellow-                                                                        orange                                   102  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH         Br Cu yellow                                   103  Cl  Cl Cl  Cl                                                                                             H  Cu brown                                    104  Cl  Cl Cl  Cl                                                                                 ##STR62##   H  Zn orange                                   105  Cl  Cl Cl  Cl                                                                                 ##STR63##   H  Cu brown                                    106  Cl  Cl Cl  Cl                                                                                 ##STR64##   H  Zn orange                                   107  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR65##   H  Ni brown                                    108  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR66##   H  Cu brown                                    109  H   H  H   H  H            H  Ni yellow                                   110  H   H  H   H  H            H  Cu yellow                                   111  H   H  H   H  H            H  Co yellow-                                                                        brown                                    __________________________________________________________________________

EXAMPLE 112

1.48 g of the bishydrazone of Example 20 are reacted in 60 ml of methylcellosolve with 0.66 g of Cu(ac)₂.H₂ O for 3 hours at 90° C. The green-yellow reaction product is filtered off while warm, washed well with methylcellosolve, alcohol and acetone and dried at 100° C. 1.55 g (93%) are obtained of a greenish-tinged yellow pigment of the formula ##STR67## which colours PVC in greenish-tinged yellow shades of outstanding fastness to light and migration.

The metal complexes of the formula ##STR68## wherein the symbols have the meaning indicated in Table IX which follows are obtained by an analogous process.

                                      Table IX                                     __________________________________________________________________________     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                          X.sub.3                                                                            X.sub.4                                                                          Y.sub.7                                                                          Y.sub.8                                                                           Y.sub.9                                                                          Y.sub.10                                                                         R   M  Shade                                         __________________________________________________________________________     113  Cl  Cl                                                                               Cl  Cl                                                                               H H  H H H   Ni yellow                                        114  Cl  Cl                                                                               Cl  Cl                                                                               H H  H H H   Cu yellow-green                                  115  Cl  Cl                                                                               Cl  Cl                                                                               H H  H H H   Zn yellow                                        116  Cl  Cl                                                                               Cl  Cl                                                                               H Cl H H H   Ni yellow                                        117  Cl  Cl                                                                               Cl  Cl                                                                               H Cl H H H   Cu yellow-green                                  118  Cl  Cl                                                                               Cl  Cl                                                                               H Cl H H H   Zn yellow                                        119  Cl  Cl                                                                               Cl  Cl                                                                               H CH.sub.3                                                                          H H H   Ni yellow-orange                                 120  Cl  Cl                                                                               Cl  Cl                                                                               H CH.sub.3                                                                          H H H   Cu yellow                                        121  Cl  Cl                                                                               Cl  Cl                                                                               H CH.sub.3                                                                          H H H   Zn yellow                                        122  Cl  Cl                                                                               Cl  Cl                                                                               H H  H Cl                                                                               H   Ni yellow                                        123  Cl  Cl                                                                               Cl  Cl                                                                               H H  H Cl                                                                               H   Cu yellow-green                                  124  Cl  Cl                                                                               Cl  Cl                                                                               H H  H Cl                                                                               H   Zn yellow                                        125  Cl  Cl                                                                               Cl  Cl                                                                               H H  Cl                                                                               Cl                                                                               H   Ni yellow                                        126  Cl  Cl                                                                               Cl  Cl                                                                               H H  Cl                                                                               Cl                                                                               H   Cu yellow-green                                  127  Cl  Cl                                                                               Cl  Cl                                                                               H H  Cl                                                                               Cl                                                                               H   Zn yellow                                        128  Cl  Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H H H   Ni yellow                                        129  Cl  Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H H H   Cu green-yellow                                  130  Cl  Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H H H   Ni yellow                                        131  Cl  Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H H H   Cu yellow-green                                  132  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H H Ni  yellow                                           133  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H H H   Cu yellow                                        134  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H CH.sub.3                                                                          H H H   Ni yellow                                                                         greenish-                                     135  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H CH.sub.3                                                                          H H H   Cu tinged yellow                                 136  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H H H   Ni yellow                                        137  Cl  Cl                                                                               Cl  Cl                                                                               H H  H H CH.sub.3                                                                           Ni yellow                                        138  Cl  Cl                                                                               Cl  Cl                                                                               H H  H H CH.sub.3                                                                           Cu yellow                                        139  Cl  Cl                                                                               Cl  Cl                                                                               H CH.sub.3                                                                          H H CH.sub.3                                                                           Ni yellow                                        140  Cl  Cl                                                                               Cl  Cl                                                                               H CH.sub.3                                                                          H H CH.sub.3                                                                           Cu yellow                                        141  Cl  Cl                                                                               Cl  Cl                                                                               H Cl H H CH.sub.3                                                                           Ni yellow-brown                                  142  Cl  Cl                                                                               Cl  Cl                                                                               H Cl H H CH.sub.3                                                                           Cu yellow-brown                                  143  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H H CH.sub.3                                                                           Ni yellow                                        144  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  H H CH.sub.3                                                                           Cu yellow                                        145  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H CH.sub.3                                                                          H H CH.sub.3                                                                           Ni yellow                                        146  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H CH.sub.3                                                                          H H CH.sub.3                                                                           Cu yellow                                        147  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H H CH.sub.3                                                                           Ni yellow                                        148  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H H CH.sub.3                                                                           Cu yellow                                        149  OCH.sub.3                                                                          Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H Cl H H CH.sub.3                                                                           Co yellow-brown                                                                   greenish-                                     150  H   H H   H H H  H H H   Ni tinged yellow                                                                  greenish-                                     151  H   H H   H H H  H H H   Cu tinged yellow                                 152  CH.sub.3 O                                                                         Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  Cl                                                                               Cl                                                                               H   Ni yellow                                                                         greenish-                                     153  CH.sub.3 O                                                                         Cl                                                                               OCH.sub.3                                                                          Cl                                                                               H H  Cl                                                                               Cl                                                                               H   Cu tinged yellow                                 154  H   H H   H H H  H H CH.sub.3                                                                           N  yellow                                        155  H   H H   H H H  H H CH.sub.3                                                                           Cu yellow-green                                  156  H   H H   H H Cl H H CH.sub.3                                                                           N  yellow                                        157  H   H H   H H Cl H H CH.sub.3                                                                           Cu yellow-green                                  158  Cl  Cl                                                                               Cl  Cl                                                                               H H  Cl                                                                               Cl                                                                               CH.sub.3                                                                           Ni orange                                        159  Cl  Cl                                                                               Cl  Cl                                                                               H H  Cl                                                                               Cl                                                                               CH.sub.3                                                                           Cu yellow                                        160  Cl  Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  H H CH.sub.3                                                                           Ni yellow                                        161  Cl  Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  H H CH.sub.3                                                                           Cu yellow                                        162  Cl  Cl                                                                               PhO Cl                                                                               H H  H H H   Ni yellow                                        163  Cl  Cl                                                                               PhO Cl                                                                               H H  H H H   Cu yellow-green                                  164  Cl  Cl                                                                               PhO Cl                                                                               H H  H H CH.sub.3                                                                           Ni yellow                                        165  Cl  Cl                                                                               PhO Cl                                                                               H H  H H CH.sub.3                                                                           Cu yellow                                        166  CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H Cl H H CH.sub.3                                                                           Ni yellow                                        167  CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H Cl H H CH.sub.3                                                                           Cu yellow-green                                  168  CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  Cl                                                                               Cl                                                                               H   Ni yellow                                        169  CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  Cl                                                                               Cl                                                                               H   Cu yellow-green                                  170  CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  Cl                                                                               Cl                                                                               CH.sub.3                                                                           Ni yellow                                        171  CH.sub.3 O                                                                         Cl                                                                               CH.sub.3 O                                                                         Cl                                                                               H H  Cl                                                                               Cl                                                                               CH.sub.3                                                                           Cu yellow                                        __________________________________________________________________________

EXAMPLE 172

2.40 g of the bishydrazone of Example 40 are reacted in 60 ml of methylcellosolve with 1.10 g of Cu(ac)₂.H₂ O for 5 hours at 90° C. The reaction product is filtered off, washed with methylcellosolve and alcohol and dried at 80° C. 2.30 g (85% of theory) are obtained of a yellow-brown pigment of the formula ##STR69## which colours PVC in yellow shades of good fastness to light and migration.

The metal complexes of the formula ##STR70## wherein the symbols have the meaning indicated in Table X which follows, are obtained by an analogous process.

                                      Table X                                      __________________________________________________________________________     Example                                                                        No.  X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.5                                                                           Y.sub.6                                                                            R.sub.6                                                                              M  Shade                                       __________________________________________________________________________     173  Cl  Cl Cl  Cl H      CH.sub.3                                                                             Ni yellow                                      174  Cl  Cl Cl  Cl H      CH.sub.3                                                                             Zn yellow                                      175  Cl  Cl Cl  Cl Cl     CH.sub.3                                                                             Ni yellow                                      176  Cl  Cl Cl  Cl Cl     CH.sub.3                                                                             Cu yellow-green                                177  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H      COOC.sub.2 H.sub.5                                                                   Ni yellow                                      178  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H      COOC.sub.2 H.sub.5                                                                   Cu yellow-brown                                179  Cl  Cl Cl  Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Ni yellow                                      180  Cl  Cl Cl  Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Cu yellow                                      181  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Ni yellow                                      182  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Cu yellow-green                                183  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   CONH.sub.2                                                                           Ni yellow                                      184  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   CONH.sub.2                                                                           Cu yellow-green                                __________________________________________________________________________

EXAMPLES 185-188

The metal complexes of the following formula ##STR71## wherein the symbols have the meaning indicated in Table XI which follows, are obtained by the methods described above from the bishydrazones of Examples 46 and 47.

                  Table XI                                                         ______________________________________                                         Example                                                                        No.    X.sub.1  X.sub.2                                                                               X.sub.3                                                                               X.sub.4                                                                             M    Shade                                  ______________________________________                                         185    Cl       Cl     Cl     Cl   Ni   yellow                                 186    Cl       Cl     Cl     Cl   Cu   yellow-green                           187    OCH.sub.3                                                                               Cl     OCH.sub.3                                                                             Cl   Ni   yellow                                 188    OCH.sub.3                                                                               Cl     OCH.sub.3                                                                             Cl   Cu   yellow-green                           ______________________________________                                    

EXAMPLES 189-197

The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Example 1 with the corresponding metal salts ##STR72##

The following table indicates the meaning of the symbols:

                  Table XII                                                        ______________________________________                                         Example                                                                        No.     Y.sub.1   Y.sub.2 Y.sub.3                                                                              Y.sub.4                                                                              M    Shade                               ______________________________________                                         189     H         H       H     H     Ni   yellow                              190     H         H       H     H     Zn   yellow                              191     H         H       H     H     Cd   yellow                              192     OC.sub.2 H.sub.5                                                                         H       H     H     Ni   orange                              193     OC.sub.2 H.sub.5                                                                         H       H     H     Zn   yellow                              194     OC.sub.2 H.sub.5                                                                         H       H     H     Cd   yellow                              195     Cl        H       Cl    H     Ni   brown                               196     Cl        H       Cl    H     Zn   yellow                              197     Cl        H       Cl    H     Cd   yellow                              ______________________________________                                    

EXAMPLE 198

1.50 g of the bishydrazone of Example 48 are heated in 70 ml of methylcellosolve with 0.63 g of Cu(ac)₂.H₂ O for 3 hours at 100° C. The yellow-green suspension is filtered hot; the filter residue is washed well with methylcellosolve, alcohol and acetone and dried at 80° C. 1.2 g (70% of theory) are obtained of a greenish-tinged yellow pigment of the formula ##STR73##

EXAMPLE 199

The procedure is as indicated in Example 198, but the bishydrazone of Example 49 is used as the starting material. The greenish-tinged yellow pigment of the formula ##STR74## is obtained.

EXAMPLE 200 Ba salt of the colorant according to Example 198

1.50 g of the bishydrazone of Example 48 are reacted in 70 ml of methylcellosolve with 0.63 g of Cu(ac)₂.H₂ O for 3 hours at 100° C. A solution of 1 g of Ba(OH)₂.8H₂ O in 20 ml of water is run dropwise into this yellow-green suspension. The reaction mixture is heated for a further 2 hours at 100° C and is then filtered hot. The filter residue is washed well with methylcellosolve, water, alcohol and acetone and dried at 90° C. 1.8 g are obtained of a yellow-green pigment which colours PVC in greenish-tinged yellow shades of good fastness to light and migration.

EXAMPLE 201

The barium salt of the copper complex of Example 199 is prepared by the process of Example 200. A pigment is obtained which colours PVC in greenish-tinged yellow shades of good fastness to light and migration.

EXAMPLE 202

The nickel complex of the same colorant is prepared by the process of Example 200. It colours PVC in yellow shades of good fastness to light and migration.

EXAMPLES 203-206

The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 56 and 57, with the corresponding metal salts. ##STR75##

The following table indicates the meaning of the symbols.

                  Table XIII                                                       ______________________________________                                         Example                                                                        No.    X.sub.1  X.sub.2                                                                               X.sub.3                                                                               X.sub.4                                                                             M   Shade                                   ______________________________________                                         203    Cl       Cl     Cl     Cl   Ni  yellow                                  204    Cl       Cl     Cl     Cl   Cu  yellow-green                            205    CH.sub.3 O                                                                              Cl     CH.sub.3 O                                                                            Cl   Ni  yellow                                  206    CH.sub.3 O                                                                              Cl     CH.sub.3 O                                                                            Cl   Cu  yellow-green                            ______________________________________                                    

EXAMPLES 207-218

The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 58-63 with the corresponding metal salts. ##STR76##

                  Table XIV                                                        ______________________________________                                         Example                                                                        No.    X.sub.1 X.sub.2                                                                              X.sub.3                                                                              X.sub.4                                                                             R     M   Shade                                ______________________________________                                         207    Cl      Cl    Cl    Cl   H     Ni  yellow                               208    Cl      Cl    Cl    Cl   H     Cu  yellow-green                         209    Cl      Cl    CH.sub.3 O                                                                           Ci   H     Ni  yellow                               210    Cl      Cl    CH.sub.3 O                                                                           Cl   H     Cu  yellow-green                         211    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl   H     Ni  yellow                               212    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           cl   H     Cu  yellow-green                         213    Cl      Cl    Cl    Cl   CH.sub.3                                                                             Ni  yellow                               214    Cl      Cl    Cl    Cl   CH.sub.3                                                                             Cu  yellow-green                         215    Cl      Cl    CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Ni  yellow                               216    Cl      Cl    CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Cu  yellow-green                         217    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Ni  yellow                               218    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Cu  yellow-green                         ______________________________________                                    

EXAMPLES 219-230

The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 50-55 with the corresponding metal salts. ##STR77##

The following table indicates the meaning of the symbols.

                  Table XV                                                         ______________________________________                                         Example                                                                        No.    X.sub.1 X.sub.2                                                                              X.sub.3                                                                              X.sub.4                                                                            Y.sub.3                                                                              M    Shade                                ______________________________________                                         219    Cl      Cl    Cl    Cl  H     Ni   yellow                               220    Cl      Cl    Cl    Cl  H     Cu   yellow-green                         221    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  H     Ni   yellow                               222    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  H     Cu   yellow-green                         223    Cl      Cl    Cl    Cl  CH.sub.3 O                                                                           Ni   yellow                               224    Cl      Cl    Cl    Cl  CH.sub.3 O                                                                           Cu   yellow-green                         225    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CH.sub.3 O                                                                           Ni   yellow                               226    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CH.sub.3 O                                                                           Cu   yellow-green                         227    Cl      Cl    Cl    Cl  Cl    Ni   yellow                               228    Cl      Cl    Cl    Cl  Cl    Cu   yellow-green                         229    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  Cl    Ni   yellow                               230    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  Cl    Cu   yellow-green                         ______________________________________                                    

EXAMPLES 231-238

The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 64-67 with the corresponding metal salts.

    ______________________________________                                          ##STR78##                                                                     Example                                                                        No.    X.sub.1 X.sub.2                                                                              X.sub.3                                                                              X.sub.4                                                                            R      M   Shade                                ______________________________________                                         231    Cl      Cl    Cl    Cl  CN     Ni  yellow                               232    Cl      Cl    Cl    Cl  CN     Cu  yellow                               233    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CN     Ni  yellow                               234    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CN     Cu  green-yellow                         235    Cl      Cl    Cl    Cl  CONH.sub.2                                                                            Ni  yellow                               236    Cl      Cl    Cl    Cl  CONH.sub.2                                                                            Cu  yellow                               237    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CONH.sub.2                                                                            Ni  yellow                               238    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CONH.sub.2                                                                            Cu  yellow-green                         ______________________________________                                    

EXAMPLES 239-245

The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 68-70 with the corresponding metal salts.

    ______________________________________                                          ##STR79##                                                                     Example                                                                        No.    X.sub.1 X.sub.2                                                                              X.sub.3                                                                              X.sub.4                                                                            R      M   Shade                                ______________________________________                                         239    Cl      Cl    Cl    Cl  CN     Ni  orange                               240    Cl      Cl    Cl    Cl  CN     Cu  yellow                               241    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CN     Ni  yellow                               242    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CN     Cu  yellow-green                         243    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CN     Co  yellow                               244    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CONH.sub.2                                                                            Ni  yellow                               245    CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CONH.sub.2                                                                            Cu  brown                                ______________________________________                                    

EXAMPLES 246-277

The metal complexes of the following formula are obtained by reacting the bishydrazones of the Examples under 1 with the corresponding metal salts.

    ______________________________________                                          ##STR80##                                                                     Ex.                                                                            No.  X.sub.1 X.sub.2                                                                              X.sub.3                                                                              X.sub. R                                                                           M           Shade                                 ______________________________________                                         246  Cl      Cl    Cl    Cl  H           Ni  red-                                                                           brown                             247  Cl      Cl    Cl    Cl  H           Cu  brown                             248  Cl      Cl    CH.sub.3 O                                                                           Cl  H           Ni  red-                                                                           brown                             249  Cl      Cl    CH.sub.3 O                                                                           Cl  H           Cu  yellow-                                                                        brown                             250  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  H           Ni  yellow-                                                                        brown                             251  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  H           Cu  yellow                            252  Cl      Cl    Cl    Cl  CH.sub.3    Ni  red-                                                                           brown                             253  Cl      Cl    Cl    Cl  CH.sub.3    Cu  brown                             254  Cl      Cl    CH.sub.3 O                                                                           Cl  CH.sub.3    Ni  red-                                                                           brown                             255  Cl      Cl    CH.sub.3 O                                                                           Cl  CH.sub.3    Cu  brown                             256  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CH.sub.3    Ni  red-                                                                           brown                             257  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl  CH.sub.3    Cu  yellow-                                                                        brown                             258  Cl      Cl    Cl    Cl                                                                                  ##STR81##  Ni  red                               259  Cl      Cl    Cl    Cl                                                                                  ##STR82##  Cu  orange                            260  Cl      Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR83##  Ni  red                               261  Cl      Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR84##  Cu  orange                            262  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR85##  Ni  red- brown                        263  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR86##  Cu  yellow-  brown                    264  Cl      Cl    Cl    Cl                                                                                  ##STR87##  Ni  red                               265  Cl      Cl    Cl    Cl                                                                                  ##STR88##  Cu  yellow- orange                    266  Cl      Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR89##  Ni  red- brown                        267  Cl      Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR90##  Cu  yellow- brown                     268  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR91##  Ni  red- brown                        269  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR92##  Cu  yellow- brown                     270  Cl      Cl    Cl    Cl                                                                                  ##STR93##  Ni  red                               271  Cl      Cl    Cl    Cl                                                                                  ##STR94##  Cu  red- brown                        272  Cl      Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR95##  Ni  red- brown                        273  Cl      Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR96##  Cu  yellow- brown                     274  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR97##  Ni  red- brown                        275  CH.sub.3 O                                                                             Cl    CH.sub.3 O                                                                           Cl                                                                                  ##STR98##  Cu  yellow- brown                     276  Cl      Cl    Cl    Cl                                                                                  ##STR99##  Ni  red                               277  Cl      Cl    Cl    Cl                                                                                  ##STR100## Cu  red- brown                        ______________________________________                                    

EXAMPLE 278

All the metal complexes described can also be prepared directly from the components, isoindolinone-3-ylidene hydrazine, hydroxy-aldehyde or hydroxy-ketone and metal salt by the one-pot method.

1.45 g of 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine, 0.945 g of 2,4-dihydroxyquinoline-3-aldehyde and 1.25 g of Ni(ac)₂.4H₂ O are reacted for 1 hour at 100° C in 50 ml of glacial acetic acid. The yellow-orange suspension is filtered at 80° C, washed well with glacial acetic acid, alcohol and acetone and dried at 80° C. 2.40 g (93% of theory) of a yellow pigment, identical with the product of Example 132, are obtained.

The formation of the metal complex can also be carried out in, for example, dimethylformamide, methylcellosolve, ethylcellosolve, Carbitol and glycol, instead of glacial acetic acid.

EXAMPLE 279

65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the colorant obtained in accordance with Example 89 are stirred together with one another and are then worked for 7 minutes at 140° C on a twin-roll calender. An orange sheet of very good fastness to light and migration is obtained.

EXAMPLE 280

1.00 g of the pigment prepared according to Example 113 is finely ground on an Engelsmann grinding machine together with 4.00 g of printer's varnish of the following composition:

    ______________________________________                                         29.4% of linseed oil-stand oil                                                                        (300 poises),                                           67.2% of linseed oil-stand oil                                                                        (20 poises),                                             2.1% of cobalt octoate                                                                               (8% of Co) and                                           1.3% of lead octoate  (24% of Pb)                                             ______________________________________                                    

and is then printed on art printing paper at 1 g/m² in the letterpress process with the aid of a block. A strong, pure shade of yellow, having good transparency and good gloss, is obtained. Very brilliant green shades can be produced in three- or four-colour printing by overprinting on blue.

The pigment is also suitable for other printing processes, such as gravure printing, offset printing and flexographic printing, and here too gives very good results. 

What we claim is:
 1. Azomethine pigments of the formula ##STR101## and metal complexes thereof, wherein A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, X₂ and X₄ denote H atoms or halogen atoms, X₁ and X₃ denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X₁ -X₄ also to be a nitro group.
 2. Azomethine pigments according to claim 1, of the formula ##STR102## wherein M denotes a divalent metal atom and A, R and X₁ -X₄ have the meaning indicated in claim
 1. 3. Azomethine pigments according to claim 2, of the formula ##STR103## wherein A₁ denotes a benzene, pyridine, pyrimidine, or pyrane radical which can also contain a fused benzene nucleus, or denotes a pyrazolone radical, R₁ denotes a hydrogen atom, M₁ denotes a copper or nickel atom, X₅ and X₇ denote H atoms or chlorine atoms or alkoxy groups containing 1-4 C atoms, and X₆ and X₈ denote H atoms or chlorine atoms, X₆ and X₈ representing chlorine atoms if X₅ and X₇ denote alkoxy groups.
 4. Azomethine pigments according to claim 3, of the formula ##STR104## wherein R₁, M₁ and X₅ to X₈ have the meaning indicated in claim 3, Y₃ and Y₄ denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro groups or groups of the formula ##EQU5## wherein M₂ denotes a Ca, Sr, Ba or Mn atom, and Z represents an O atom or an imino group.
 5. Azomethine pigments according to claim 4, of the formula ##STR105## wherein R₁, M₁, X₅ to X₈, Y₃ and Y₄ have the meaning indicated in claims 3 and
 4. 6. Azomethine pigments according to claim 3, of the formula ##STR106## wherein M₁ and X₅ to X₈ have the meaning indicated in claim 3, and R₃ denotes nitrile or a carbamoyl group.
 7. Azomethine pigments according to claim 3, of the formula ##STR107## wherein M₁ and X₅ to X₈ have the meaning indicated in claim 3, and R₄ denotes nitrile or a carbamoyl group.
 8. Azomethine pigments according to claim 3, of the formula ##STR108## wherein M₁ and X₅ to X₈ have the meaning indicated in claim 3, and R₅ denotes a hydrogen atom or a lower alkyl group or an aryl group. 